{"id":12825,"date":"2014-08-10T12:05:58","date_gmt":"2014-08-10T11:05:58","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=12825"},"modified":"2014-08-10T15:34:48","modified_gmt":"2014-08-10T14:34:48","slug":"using-a-polar-bond-to-flip-on-the-knife-edge","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=12825","title":{"rendered":"Using a polar bond to flip: on the knife-edge!"},"content":{"rendered":"
\n

In my\u00a0first post<\/a> on the topic, I discussed how inverting the polarity of the C-X bond from X=O to X=Be (scheme below) could flip the stereochemical course of the electrocyclic pericyclic reaction of a divinyl system. This was followed up<\/a> by exploring what\u00a0happens at the half way stage, i.e.<\/em> X=CH2<\/sub>, the answer being that\u00a0one gets an antarafacial<\/em><\/strong> pathway as with X=O. Here I fill in another gap, X=BH to see if a metaphorical microscope can be used to view the actual region of the “flip” to a suprafacial<\/em><\/strong> mode.\"divinylketon\"<\/a> This time, uniquely, it proved possible to locate TWO transition states for this process, one suprafacial<\/em>[1]<\/a><\/span> and one antarafacial<\/em>[2]<\/a><\/span>, this latter being 10.5 kcal\/mol lower in \u0394G\u2020<\/sup> (\u03c9B97XD\/6-311G(d,p)\/SCRF=dichloromethane). It is quite rare to be able to find BOTH stereochemical outcomes of a thermal pericyclic reaction.\u2021<\/sup><\/p>\n

First, the antarafacial IRC (X=BH)[3]<\/a><\/span>. There are several interesting features. Note at IRC = -8, the divinyl compound appears as a Hidden Intermediate<\/strong> <\/em>(HI), having formed from a compound where the HB=C substituent has ring opened from a cyclobutene-like precursor (initial electrocyclic). If you watch the animation, you can see the antarafacial bond\u00a0forming from the bottom<\/strong> face of the vinyl group on the left to the top<\/strong> face of the vinyl group in the HI on the right (antarafacial=conrotation). Because the entire process is concerted (no real intermediates participate), we have here an unusual pericyclic cascade<\/em> where one electrocyclic reaction is immediately followed by another quite different one.\"BH-antaraa\"<\/a> \"BH-antara\"<\/a> \"BH-antaraG\"<\/a> Now for the suprafacial IRC[4]<\/a><\/span>. It is pretty similar to the previous path, but again if you inspect very carefully you will see that it is the TOP<\/strong> face of the vinyl group on the left forming the bond to the TOP<\/strong> face of the vinyl group on the right (suprafacial\/disrotation). \"BH-supraa\"<\/a>\"BH-supra\"<\/a>\"BH-supraG\"<\/a> You might ask if the molecules used here are realistic, i.e.<\/em> could they form the basis of real reactions to be conducted in a laboratory? Well, the C=B-C fragment has 9 hits in the CCDC crystal database (none for C=B-H). One example is cited here.[5]<\/a><\/span>. So, yes, possibly a realistic system, except the barriers do look too high. Perhaps suitable substituents might help? But even if this could not be carried out in a test-tube,\u00a0it does teach one about pericyclic reactions and how one might manipulate them.<\/p>\n

\n

\u2021<\/sup>One such is the [1,6] sigmatropic shift in homotropylium cation involving migration of a Me2<\/sub>C+<\/sup> group, where the “allowed” process in which the migrating group retains its configuration has a barrier of 17.7 kcal\/mol and the “forbidden” route where the migrating group inverts its configuration with a barrier of 38.6 kcal\/mol (thanks to Alex Genaev; I will strive to make the coordinates available via<\/em> the repository shortly).<\/p>\n

References<\/h2>\n
  1. H.S. Rzepa, \"Gaussian Job Archive for C5H7B\", 2014. https:\/\/doi.org\/10.6084\/m9.figshare.1133933<\/a>\n\n<\/li>\n
  2. H.S. Rzepa, \"Gaussian Job Archive for C5H7B\", 2014. https:\/\/doi.org\/10.6084\/m9.figshare.1133934<\/a>\n\n<\/li>\n
  3. H.S. Rzepa, \"Gaussian Job Archive for C5H7B\", 2014. https:\/\/doi.org\/10.6084\/m9.figshare.1133936<\/a>\n\n<\/li>\n
  4. H.S. Rzepa, \"Gaussian Job Archive for C5H7B\", 2014. https:\/\/doi.org\/10.6084\/m9.figshare.1134015<\/a>\n\n<\/li>\n
  5. M. Menzel, H.J. Winkler, T. Ablelom, D. Steiner, S. Fau, G. Frenking, W. Massa, and A. Berndt, \"Diborylcarbenes as Reactive Intermediates in Double 1,2\u2010Rearrangements with Low Activation Enthalpies\", Angewandte Chemie International Edition in English<\/i>, vol. 34, pp. 1340-1343, 1995. https:\/\/doi.org\/10.1002\/anie.199513401<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

    In my\u00a0first post on the topic, I discussed how inverting the polarity of the C-X bond from X=O to X=Be (scheme below) could flip the stereochemical course of the electrocyclic pericyclic reaction of a divinyl system. This was followed up by exploring what\u00a0happens at the half way stage, i.e. X=CH2, the answer being that\u00a0one gets […]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"jetpack_post_was_ever_published":false,"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"activitypub_content_warning":"","activitypub_content_visibility":"","activitypub_max_image_attachments":5,"activitypub_interaction_policy_quote":"anyone","activitypub_status":"","footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2}},"categories":[559,1086],"tags":[1250,1249,1251],"ppma_author":[2661],"class_list":["post-12825","post","type-post","status-publish","format-standard","hentry","category-pericyclic","category-reaction-mechanism-2","tag-alex-genaev","tag-hawaii","tag-hb"],"yoast_head":"\nUsing a polar bond to flip: on the knife-edge! - Henry Rzepa's Blog<\/title>\n<meta name=\"robots\" content=\"index, follow, max-snippet:-1, max-image-preview:large, max-video-preview:-1\" \/>\n<link rel=\"canonical\" href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=12825\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Using a polar bond to flip: on the knife-edge! - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"In my\u00a0first post on the topic, I discussed how inverting the polarity of the C-X bond from X=O to X=Be (scheme below) could flip the stereochemical course of the electrocyclic pericyclic reaction of a divinyl system. This was followed up by exploring what\u00a0happens at the half way stage, i.e. X=CH2, the answer being that\u00a0one gets […]\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=12825\" \/>\n<meta property=\"og:site_name\" content=\"Henry Rzepa's Blog\" \/>\n<meta property=\"article:published_time\" content=\"2014-08-10T11:05:58+00:00\" \/>\n<meta property=\"article:modified_time\" content=\"2014-08-10T14:34:48+00:00\" \/>\n<meta property=\"og:image\" content=\"http:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2014\/08\/divinylketon.svg\" \/>\n<meta name=\"author\" content=\"Henry Rzepa\" \/>\n<meta name=\"twitter:card\" content=\"summary_large_image\" \/>\n<meta name=\"twitter:label1\" content=\"Written by\" \/>\n\t<meta name=\"twitter:data1\" content=\"Henry Rzepa\" \/>\n\t<meta name=\"twitter:label2\" content=\"Estimated reading time\" \/>\n\t<meta name=\"twitter:data2\" content=\"2 minutes\" \/>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"Using a polar bond to flip: on the knife-edge! - Henry Rzepa's Blog","robots":{"index":"index","follow":"follow","max-snippet":"max-snippet:-1","max-image-preview":"max-image-preview:large","max-video-preview":"max-video-preview:-1"},"canonical":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=12825","og_locale":"en_GB","og_type":"article","og_title":"Using a polar bond to flip: on the knife-edge! - Henry Rzepa's Blog","og_description":"In my\u00a0first post on the topic, I discussed how inverting the polarity of the C-X bond from X=O to X=Be (scheme below) could flip the stereochemical course of the electrocyclic pericyclic reaction of a divinyl system. 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An obvious question would be: what happens at the half way stage, ie X=CH2? Well,\u2026","rel":"","context":"In "pericyclic"","block_context":{"text":"pericyclic","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=559"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":12782,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=12782","url_meta":{"origin":12825,"position":1},"title":"Using a polar bond to flip the (stereochemical) outcome of a pericyclic reaction.","author":"Henry Rzepa","date":"August 4, 2014","format":false,"excerpt":"The outcome of pericyclic reactions con depend most simply on three conditions, any two of which determine the third. Whether the catalyst is \u0394 or h\u03bd (heat or light), the topology determining any stereochemistry and the participating electron count (4n+2\/4n). It is always neat to conjure up a simple switch\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":20354,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=20354","url_meta":{"origin":12825,"position":2},"title":"Epoxidation of ethene: a new substituent twist.","author":"Henry Rzepa","date":"December 21, 2018","format":false,"excerpt":"Five years back,\u00a0I speculated about the mechanism of the epoxidation of ethene by a peracid, concluding that kinetic isotope effects provided interesting evidence that this mechanism is highly asynchronous and involves a so-called \"hidden intermediate\". Here I revisit this reaction in which a small change is applied to the atoms\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2018\/12\/imine2.gif?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]},{"id":12895,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=12895","url_meta":{"origin":12825,"position":3},"title":"Computationally directed synthesis: 2,3-dimethyl-2-butene + NO(+).","author":"Henry Rzepa","date":"September 6, 2014","format":false,"excerpt":"In the previous posts, I explored reactions which can be flipped between two potential (stereochemical) outcomes. This triggered a memory from Alex, who pointed out this article from 1999 in which the nitrosonium cation as an electrophile can have two outcomes A or B when interacting with the electron-rich 2,3-dimethyl-2-butene.\u2026","rel":"","context":"In "pericyclic"","block_context":{"text":"pericyclic","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=559"},"img":{"alt_text":"NOa","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2014\/09\/NOa.gif?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":11642,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=11642","url_meta":{"origin":12825,"position":4},"title":"Avoided (pericyclic) anti-aromaticity: Reactions of t-butyl-hydroxycarbene.","author":"Henry Rzepa","date":"November 13, 2013","format":false,"excerpt":"Not long ago, I described a cyclic carbene in which elevating the carbene lone pair into a \u03c0-system transformed it from a formally 4n-antiaromatic \u03c0-cycle into a 4n+2 aromatic \u03c0-cycle. From an entirely different area of chemistry, another example of this behaviour emerges; Schreiner's trapping and reactions of t-butyl-hydroxycarbene, as\u2026","rel":"","context":"In "pericyclic"","block_context":{"text":"pericyclic","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=559"},"img":{"alt_text":"H-mig","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/11\/H-mig.gif?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":4592,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=4592","url_meta":{"origin":12825,"position":5},"title":"The stereochemistry of [8+2] pericyclic cycloadditions.","author":"Henry Rzepa","date":"July 10, 2011","format":false,"excerpt":"Steve Bachrach has blogged on the reaction shown below. If it were a pericyclic cycloaddition, both new bonds would form simultaneously, as shown with the indicated arrow pushing. Ten electrons would be involved, and in theory, the transition state would have 4n+2 aromaticity. In fact\u00a0Fernandez, Sierra and Torres have reported\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2011\/07\/2%2B8.jpg?resize=350%2C200","width":350,"height":200},"classes":[]}],"jetpack_likes_enabled":false,"authors":[{"term_id":2661,"user_id":1,"is_guest":0,"slug":"admin","display_name":"Henry Rzepa","avatar_url":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","0":null,"1":"","2":"","3":"","4":"","5":"","6":"","7":"","8":""}],"_links":{"self":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/12825","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=12825"}],"version-history":[{"count":20,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/12825\/revisions"}],"predecessor-version":[{"id":12851,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/12825\/revisions\/12851"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=12825"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=12825"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=12825"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=12825"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}